TW200936648A - Polysiloxane, method for producing the same, and method for producing cured product of the same - Google Patents

Abstract

Disclosed is a polysiloxane which is in a liquid form having a low viscosity. This polysiloxane has excellent curability, and a cured product thereof has excellent heat resistance. Also disclosed are a method for producing such a polysiloxane, and a method for producing a polysiloxane cured product by using such a polysiloxane. Specifically disclosed is a polysiloxane which is characterized by being obtained by hydrolyzing/polycondensing a silicon compound having three hydrolyzable groups, a silicon compound having two hydrolyzable groups and a silicon compound having one hydrolyzable group. The polysiloxane is also characterized by containing a hydrosilylatable carbon-carbon unsaturated group, a hydrosilyl group and an alkoxysilyl group, and having a number average molecular weight of 500-20,000.

Description

200936648 IX. Description of the Invention [Technical Field] The present invention relates to a polyoxyalkylene having a carbon-carbon unsaturated group and a hydrogen group based on a hydrosilyl hydrazine reaction. Further, the method for producing the polyoxyalkylene is described. Further, it is a method for producing a cured product of the polyoxyalkylene. The cured product of the polyoxyalkylene can be used as a heat-resistant material. [Prior Art] A polyoxyalkylene having a carbon-carbon unsaturated group and a hydrogen group capable of hydrogenation reaction is known (see Patent Documents 1 to 4). In the past, polyoxyalkylenes, for example, even at a lower viscosity of less than 30,000 mPa.s at 25 ° C, the resulting 5% weight loss temperature in the cured product is a high 900 ° C level, not exceeding 1 000 ° C, its heat resistance is not sufficient. Therefore, there is no liquid substance having a low viscosity and a polysiloxane having a high heat resistance of the obtained cured product.专利 专利 06 06 06 06 06 06 06 06 06 06 08 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 In the present invention, it is an object of the present invention to provide a polyoxyalkylene which satisfies a low-viscosity liquid material and has excellent hardening workability and excellent heat resistance of the obtained cured product. Further, it is an object of the invention to provide a method for producing a cured product of polyoxyalkylene-5-200936648 using the polyoxyalkylene. In order to solve the above problems, the present invention is as follows. A polyoxane which is a ruthenium compound (T) having three hydrolyzable groups, a sand compound (d) having two hydrolyzable groups, and a ruthenium compound (Μ) having one hydrolyzable group. a polyoxyalkylene obtained after the hydrolysis/polycondensation reaction, characterized by

At least one of the sand compound (Τ), the chopping compound (d), and the sand compound (Μ) has an anthracene hydrogen group, and the sand compound (Τ), the above-mentioned anthracene compound (d), and the above-mentioned anthracene compound (Μ) At least one carbon-carbon unsaturated group having a hydrogenation reaction, and the polyoxyalkylene has a carbon-carbon unsaturated group, a hydrazine group and an alkoxy group having a hydrogenation reaction, and the number average molecular weight is 500. ~20000. 2. The polyoxyalkylene according to the above 1, which comprises the following general formula (1);

[化1 H—(Α—(ROnSiO^

(1) wherein A is an organic group having 2 to 10 carbon atoms having a carbon-carbon unsaturated group capable of hydrogenation, R1 is an alkyl group having 1 to 20 carbon atoms, and 2 is a carbon number of 6 to 20 a valence aromatic group or a divalent alicyclic group having 3 to 20 carbon atoms, n is ruthenium or 1, R 2 is a hydrogen atom, a carbon number of 1 to 10, or a carbon-carbon having a sand-hydrogenation reaction An organic group having a carbon number of 2 to 10 on a saturated basis (R 2 in 1-6 - 200936648 may be the same or different), and R 3 is a hydrogen atom or a carbon number of a carbon-carbon unsaturated group having a hydrogenation reaction. An organic group of ～10, R 4 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an organic group having a carbon number of 2 to 1 Å having a carbon-carbon unsaturated group capable of hydrogenation reaction (R4 in 1 molecule) For the same or different) 'R5 is an alkyl group having 1 to 6 carbon atoms, and v, x, y and z are positive numbers 'w is 0 or a positive number, 〇.〇〇lgx/(v + w) €2,0.01' y/(v + w )'2, O.Ol^z/ ( v + w + x + y) $1. However, when w = 0, at least one of R2, R3 〇 and R4 is an organic group having 2 to 10 carbon atoms which has a carbon-carbon unsaturated group which can be hydrogenated. A method for producing a polyoxaxane according to the above aspect, which is characterized in that it comprises a ruthenium compound (T) having three hydrolyzable groups and has two hydrolyzability. The base compound (D) and the hydrazine compound (M) having one hydrolyzable group are subjected to hydrolysis in the presence or absence of an organic solvent, and the first step of the polycondensation reaction, the above hydrazine compound (T), the above At least one of the ruthenium compound (D) and the ruthenium compound (M) has an anthracene hydrogen group, and at least one of the ruthenium compound (T), the ruthenium compound (D), and the ruthenium compound (M) has an anthracene. A carbon-carbon unsaturated group of a hydrogenation reaction. 4. The method for producing a polyoxosiloxane according to the above 3, wherein the hydrolyzable group of the ruthenium compound (T) is an alkoxy group, and the hydrolyzable group of the ruthenium compound (〇) is an alkoxy group. The hydrolyzable group which the compound (Μ) has is an alkoxy group or a decyloxy group. 5. The method for producing a polyoxyalkylene according to the above 3 or 4, wherein after the first step, the water is distilled in the presence of a solvent containing an aromatic hydrocarbon of 200936648 having a boiling point of 90 ° C or higher. Go to the second step. 6. The method for producing a polyoxyalkylene according to any one of the above 3 to 5, wherein the polyoxyalkylene has a structure represented by the following general formula (2). [Chemical 2]

Wherein A is an organic group having 2 to 10 carbon atoms of a carbon-carbon unsaturated group capable of hydrogenation, R1 is an alkylene group having 1 to 20 carbon atoms, and a divalent aromatic having 6 to 20 carbon atoms; a base or a divalent alicyclic group having a carbon number of 3 to 20 η is hydrazine or 1, R 2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon-carbon unsaturated group having a hydrogenation reaction. An organic group having 2 to 10 carbon atoms (R2 in one molecule may be the same or different), and R3 is a hydrogen atom or an organic group having 2 to 10 carbon atoms having a carbon-carbon unsaturated group capable of hydrogenation reaction, R4 Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an organic group having 2 to 10 carbon atoms having a carbon-carbon unsaturated group capable of hydrogenation reaction (R4 in 1 molecule may be the same or different), R5 The alkyl group 'v'x'y and z with a carbon number of 1 to 6 are positive numbers, w is 0 or a positive number, 0.001Sx/(v + w) $2, 0.01Sy/(v + w )* O.Ol^z / ( v + w + x + y ) $1. However, when w = 0, at least one of R2, R3 and R4 is an organic group having 2 to 10 carbon atoms which has a carbon-carbon unsaturated group which can be hydrogenated. 7. A method for producing a polyoxyalkylene cured product, characterized in that the polypyroxane described in the above 1 is contained in a non-existing catalyst for a hydrogenation reaction, and is more than 150 ° C or more. The step of heating at a temperature below °C. 200936648 8. A method for producing a polyoxymethane cured product, comprising the steps of: carrying out the following steps, wherein the polyoxyalkylene described in the above 1 is in the absence of a catalyst for hydrogenation reaction, The step of heating at a temperature of 50 ° C or more and less than 15 (TC) and the step of heating at a temperature of 150 ° C or higher and 700 ° C or lower. The polyoxyalkylene of the present invention is 25°. C has a low viscosity of 30,000 mPa·s or less and can be hardened without a catalyst. Further, the cured product is reduced by 5% by weight, and the temperature is above 10 °C, which imparts excellent heat resistance and no fracture. The method for producing a polyoxyalkylene of the present invention is to efficiently produce a polyoxyalkylene having the above-described excellent properties. Further, the method for producing a cured polysiloxane of the present invention does not need to be used. The catalyst can efficiently produce a cured product excellent in heat resistance. BEST MODE FOR CARRYING OUT THE INVENTION The polyoxyalkylene of the present invention has two compounds (T) having three hydrolyzable groups, and two Hydrolyzable group of ruthenium compound (D) and having one hydrolyzable group The compound (Μ) is obtained by hydrolysis or polycondensation reaction, and has a carbon-carbon unsaturated group capable of hydrogenation reaction, a hydrogen group (a group having a Si-fluorene bond), and an alkoxy group, and the number average molecular weight is The compound of the range of 500 to 2 0000. The polyoxyalkylene of the present invention is derived from the above ruthenium compounds (T), (D) and (M), and contains a sesquisesquioxane unit (hereinafter referred to as "structural unit T". a compound of a polyoxygen unit (hereinafter referred to as "structural unit D") and a monofunctional siloxane unit (hereinafter referred to as "structure sheet-9-200936648 Μ"). Further, the above ruthenium compound (T) And at least one of (D) and (M) has an anthracene hydrogen group, and at least one of these compounds is a carbon-carbon unsaturated group having a hydrogenation reaction. The unsaturated group is generally bonded to ruthenium. An organic group having a carbon number of 2 to 10 having a double bond or a bond bond on the atom. Specific examples of the unsaturated group include a vinyl group, an o-styryl group, a methylstyryl group, and a p-styryl group. Propylene fluorenyl, methacryl fluorenyl, acryloxy, methacryloxy, 1-propenyl, 1-butyl 1, 1-pentenyl, 3-methyl-1-butenyl, phenylvinyl, vinyl, 1-propenyl, 1-butenyl, 1-pentenyl, 3-methyl- In the fluorene compound having the above unsaturated group, the number of the unsaturated groups may be one or two or more. When two or more unsaturated groups are present These unsaturated groups may be the same or different from each other. Further, two or more unsaturated groups may be bonded to the same atom or bonded to a plurality of germanium atoms. However, bonding is carried out on the same germanium atom. When the polysiloxane of the unsaturated group is hardened, the unreacted ethylene group which is caused by steric hindrance is likely to remain, so that heat resistance is insufficient. Therefore, the ruthenium compound having the above unsaturated group is preferably a compound in which one of the above unsaturated groups is bonded to one ruthenium atom. The hydrolyzable group in the above ruthenium compounds (T), (D) and (M) is bonded to a ruthenium atom, and a functional group or atom of a stanol group can be formed by a hydrolysis reaction. Examples of the hydrolyzable group include an alkoxy group, a decyloxy group, and a halogen atom. From the viewpoints of easy availability of raw materials and good reactivity, 'methoxy, ethoxy, propoxy, decyloxy and chlorine atoms are good. -10-200936648 Good hydrolysis group, methoxy, ethoxy The base and the methylalkoxy group are particularly preferred hydrolyzable groups. However, the above-mentioned oxime compound has a hydroxyl group, and when the hydroxy group is bonded to a ruthenium atom, a stanol group is formed from the beginning, and the hydroxy group is not a functional group which can form a sand-based alcohol group by a hydrolysis reaction. However, the compound having a warp group in the present invention can be regarded as the same substance as the hydrolyzed compound having a hydrolyzable group (the former of the polycondensation reaction).矽 The ruthenium compound (τ) having three hydrolyzable groups is a component of the structural unit T (sandaperane unit) which is a constituent unit of the polyoxyalkylene produced by the hydrolysis and polycondensation reaction. The ruthenium compound (τ) is preferably a compound containing one ruthenium atom and three hydrolyzable groups bonded to the ruthenium atom. The ruthenium compound (T) is an important component for making the cured polysiloxane oxide excellent in heat resistance. Examples of the ruthenium compound (T) include a ruthenium compound having a ruthenium hydrogen group (hereinafter referred to as "ruthenium compound (TH)"), and a ruthenium compound having a carbon-carbon unsaturated group capable of hydrogen oximation reaction ( Hereinafter, it is called "anthraquinone compound (TU)"). These may be used alone or in combination of two or more. Examples of the ruthenium compound (TH) include trimethoxy decane, triethoxy decane, tripropoxy decane, and trichlorodecane. Examples of the ruthenium compound (TU) include trimethoxyvinyl decane, triethoxyvinyl decane, tripropoxy vinyl decane, trichloroethylene decane, trimethoxy (4-vinylphenyl) decane, and three. Ethylene (4-vinylphenyl) decane, tripropoxy (4-vinylphenyl) decane, trichloro (4-ethyl-11 - 200936648 enephenyl) decane, etc. An anthracene compound having an unsaturated group such as a vinyl group, an acryloyl group or a methacryl group. Examples of the ruthenium compound (T) other than the ruthenium compound (TH) and the ruthenium compound (TU) (hereinafter referred to as "ruthenium compound (TO)") include trimethoxyalkyl decane and triethoxyalkyl group. Of decane, tripropoxyalkyl decane, trichloroalkyl decane, trimethoxyphenyl decane, triethoxy phenyl decane, tripropoxy phenyl decane, trichlorophenyl decane; and among these compounds, The alkyl group or the phenyl group to which the ruthenium atom is bonded is a trialkoxy decane or the like which is substituted with a group or an atom other than the carbon-carbon unsaturated group of the hydrogenation reaction. The above-mentioned ruthenium compound (T) is preferably one containing a ruthenium compound (TH) from the viewpoint of obtaining a cured product having remarkably excellent heat resistance. The ruthenium compound (D) having two hydrolyzable groups is a component of the structural unit D (polyoxymethylene unit) as a constituent unit of the polyoxyalkylene produced by the hydrolysis/polycondensation reaction. The ruthenium compound (D) is preferably a compound containing one ruthenium atom and two hydrolyzable groups bonded to the ruthenium atom. The ruthenium compound (D) suppresses the viscosity of the polyoxyalkylene to a small amount, and is an important component for forming a good film of the cured polysiloxane. Examples of the ruthenium compound (D) include an anthracene compound having an anthracene hydrogen group (hereinafter referred to as "anthracene compound (DH)"), and a ruthenium compound having a carbon-carbon unsaturated group capable of hydrogenation reaction (hereinafter referred to as "anthracene compound (DH)"). It is "矽 compound (DU)"). These may be used singly or in combination of two or more kinds as examples of the hydrazine compound (DH), and examples thereof include dimethoxymethyl 200936648 decane, diethoxymethyl decane, dipropoxymethyl decane, and dichloromethyl. Base decane and the like. Examples of the ruthenium compound (DU) include a compound ruthenium having an unsaturated group such as a vinyl group, an ethyl group, a propylene group or a methyl propyl group, and the ruthenium compound (DH) and a ruthenium compound (DU). Examples of the sand compound (D) other than the compound (hereinafter referred to as "anthracene compound (DO)") include dimethoxydialkylnonane, diethoxydialkylnonane, and dipropoxy group. Alkyl decane, dichlorodialkyl decane, dimethoxydiphenyl decane, diethoxydiphenyl decane, dipropoxydiphenyl decane, dichlorodiphenyl decane; and among these compounds, The dialkoxy decane which is bonded to the alkyl group of the ruthenium atom or the phenyl group is substituted by a group or an atom other than the carbon-carbon unsaturated group which can be hydrogenated. The ruthenium compound (Μ) having one hydrolyzable group is a component of the structure 〇 unit Μ (-functional siloxane structure unit) which is a constituent unit of the polysiloxane which is formed by the hydrolysis/polycondensation reaction. . The ruthenium compound (Μ) suppresses the viscosity of the polyoxyalkylene to a small amount, and is an important component for forming a good film by hardening the polysiloxane. The ruthenium compound (Μ) may contain one ruthenium atom, or may be a ruthenium compound having one hydrolyzable group bonded to a ruthenium atom (hereinafter referred to as "monomer (Ml)"), or may have two ruthenium compounds. The monomer (M1) is hydrolyzed and condensed to form a one-molecular ruthenium compound (hereinafter referred to as "ruthenium dimer (M2)"). When the ruthenium compound (M) is a ruthenium dimer (M2), two structural units Μ can be formed from one molecule of the ruthenium compound (M). -13- 200936648 As an example of the sand compound (Μ), a cerium compound having a sand-hydrogen-based compound (hereinafter referred to as "anthracene compound") and a carbon-carbon unsaturated group having a catalyzable reaction (hereinafter referred to as It is called "smoke (MU)" and so on. These can be used alone or in combination of two. Examples of the ruthenium compound (ΜΗ) include methoxy dioxane, ethoxy dimethyl decane, propoxy dimethyl decane, chlorodioxane, and 1,1,3,3-tetramethyl group. Oxane and the like. In the exemplified, 1,1 tetramethyldioxane is a ruthenium dimer (M2), and other than this, it is 矽 (Ml). Examples of the ruthenium compound (MU) include methoxyethylmethyl decane, ethoxyethylene dimethyl decane, propoxy ethylene dimethane, vinyl chloride dimethyl decane, and 1,3-diethylene tetra In the case of methyl dioxane, 1,3-diethylenetetramethyldioxane is a ruthenium dimer, and other than oxime monomer (Ml). Further, when the ruthenium compound (MH) and the ruthenium compound (MU) are used as the ruthenium compound, the heat resistance of the obtained polyoxyalkylene cured product tends to be inferior, so that it is not preferably used. The ratio of the ruthenium compound (T), the ruthenium (D), and the ruthenium compound (M) used in the hydrolysis/polycondensation reaction is based on the total amount of the ruthenium compound (τ), the compound (D), and the ruthenium compound (M). Each is 80% Mo, % 1 to 3 Mo Mo % and 5 to 5 Mo Mo. /. Preferably, it is preferably 75 mol%, 2 25 mol%, and 1〇45 45 mol%, preferably 70 mol%, 2-20 mol%, and 15-40 mol%. . However, the hydrazine is hydrogenated to give methylmethyl, 3,3-monomer, enedionyl, and the like. (M2 external compound 矽化30~ 4 0~ 50~ , sand 200936648 The compound (Μ) is a ratio of the 矽 compound (μ) when the ruthenium dimer (M2) is contained, which is suitable for the ruthenium dimer (Μ2) The amount used is converted to the ratio of the amount of the hydrazine monomer (M1) used. For example, the ruthenium dimer (M2) 1 mole corresponds to the oxime compound (M) 2 mole fraction. The same applies to the following description of the specification. Ruthenium compound (M) 'Use a ruthenium dimer (M2) having a structure in which two fluorene monomers (M1) are condensed (for example, '1,1,3,3-tetramethyldi-Q-oxane, 1, 3-diethylenetetramethyldioxane, etc.] As described above, the oxime dimer (M2) 1 mole corresponds to oxime monomer (Ml) 2 moles. However, ruthenium dimer (M2) The reactivity for hydrolysis is relatively small, and the reaction conditions are not hydrolyzed in about half or unreacted, so the amount of loading must be more than the ratio assumed in the chemical quantity reaction. Ml), hydrazine compound (T) and hydrazine compound (D) When the above ratio is used, the reaction is carried out almost in the form of a stoichiometric amount, and is substantially provided in the total amount of the reaction (of course, When the ratio of use of the ruthenium compound (T) is too small, the obtained cured polyoxymethane has a tendency to deteriorate in heat resistance. On the other hand, when it is too large, sometimes When the polypyrene is used as a higher viscosity or the film obtained by hardening the polyoxyalkylene is liable to be broken, when the ratio of the use of the antimony compound (D) is too small, the obtained polyoxane becomes a higher viscosity. The film obtained by hardening the polyoxyalkylene oxide is liable to be broken. On the other hand, the polyoxymethane hardened product tends to have heat resistance deterioration. -15- 200936648 When the use ratio of the antimony compound (Μ) is too small, the resulting polycondensation The oxime will become a higher viscosity or the film obtained by curing the polyoxy siloxane will be easily broken. On the other hand, the shale oxide has a tendency to deteriorate in heat resistance. Moreover, as described above, bismuth compound (Τ) Among them, the ruthenium compound (ΤΗ) is the most important component for improving the heat resistance of the cured polyoxymethane. The ratio of the ruthenium compound (ΤΗ) used in the hydrolysis/polycondensation reaction is 矽The total amount of the compound (Τ), the ruthenium compound (D) and the ruthenium compound (Μ) is preferably 30 to 80 mol%, preferably 35 to 75 mol%, and 4 to 7 More preferably, the polyoxane of the present invention is a carbon-carbon unsaturated group, an anthracene hydrogen group and an alkoxyfluorenyl group having a hydrogenation-reactive reaction in the molecule. Heating the polysiloxane of the present invention In the case of an alkane, a carbon-carbon unsaturated group which can be hydrogenated by a polyoxyalkylene, and a hydrogen group which is contained in another polyoxyalkylene can be hardened by hydrogenation, thereby obtaining a hardening excellent in heat resistance. In the polyoxyalkylene of the present invention, the number of the fluorene-hydrogen groups contained in one molecule is preferably from 1 to 10 times the number of the carbon-carbon unsaturated groups which can be hydrogenated, preferably from 2 to 2. 9 times is preferred, 3 to 8 times is better, and 4 to 7 times is particularly good. The reason is that when the polyoxyalkylene is hardened by a hydrogenation reaction, if the carbon-carbon unsaturated is left unreacted, the cured product is insufficient in heat resistance, so it is necessary not to make carbon-carbon. The amount of the hydrazine group in the amount of the saturated group is an excess amount. Further, it is necessary to avoid the excess of the ratio of the hydrogen group to be necessary. For example, polyoxyalkylene-16-200936648, which contains too much hydrazine based on a hydrazine compound (ΤΗ), may gel or become a high viscosity. Further, in the case of a polyoxyalkylene containing a hydrazine hydrogen group derived from a sand compound (MH), when the sand hydrogen group derived from the hydrazine compound (MH) is largely unreacted and left, the heat resistance of the obtained cured product may not be obtained. Full case. The alkoxyfluorenyl group is not particularly limited, but is usually an alkoxyfluorenyl group having 1 to 6 carbon atoms. From the viewpoints of the stability of the polyoxyalkylene and the good reaction balance with the curing of the polyoxyalkylene, the ethoxylated fluorenyl group, the η-propoxy fluorenyl group and the isopropoxy fluorenyl group are preferred. Isopropoxy fluorenyl is particularly preferred. Further, the compound derived from the alkoxyfluorenyl group contained in the polyoxyalkylene of the present invention is not particularly limited. The alkoxyfluorenyl group may be an unreacted alkoxyfluorenyl group derived from the above hydrazine compound. Further, when an alcohol is used as the solvent for the hydrolysis/polycondensation reaction, the alcohol can be reacted with a hydrazine compound or the like to form an alkoxy fluorenyl group, and thus the alkoxy fluorenyl group can be used. The alkoxy group containing an alkoxyfluorenyl group is excellent in the stability of the polyoxyalkylene oxide and the reactivity at the time of curing the polyoxyalkylene oxide, and is preferably an ethoxy group, an η-propoxy group and an isopropyl group. The oxy group is preferably oxime or isopropoxy group. Since the polyoxyalkylene of the present invention has an alkoxyfluorenyl group, the selectivity of the curing conditions of the polyoxyalkylene can be expanded, and excellent hardening workability can be obtained. For example, when the polyoxyalkylene is partially hardened at a temperature lower than 150 ° C, and the hardening is performed at a temperature of 150 ° C or higher and 70 ° C or lower, the operation of the sample in the previous stage becomes easy. The polyoxosiloxane of the present invention contains at least the following constituent units (i) and (ii) by the reaction of the above ruthenium compounds (T), (D) and (Μ). The polyoxyalkylene of the present invention is The other constituent unit may contain the following structural unit -17-200936648 (iii). Further, the alkoxy fluorenyl group having the polyoxyalkylene oxide of the present invention may be contained in any one of the following constituent units. Unit of hydrazine hydrogen group • Constituent unit (Π): unit of carbon-carbon unsaturated group capable of hydrogenation reaction • Component unit (iii): carbon-carbon unsaturated group having no hydrogen group and hydrogenation reaction The unit is intended to make the obtained cured product excellent in heat resistance, and the ratio of the total number of constituent units (i) and (ii) of 0 in the polyoxane is such that the constituent units (i) and (Π) and (iii) The total number is based on 70% or more, preferably 80% or more. 5% or more is more preferably 90% or more. The above-mentioned constituent unit (i) is exemplified by the following three types. The polyoxyalkylene of the present invention may contain only one type of constituent unit or contain Two or three types, and when they contain a plurality of constituent units, they may be the same or different from each other. (HS1O3/2 ) ❹ [Chemical 3]

[R2 is a hydrogen atom or an alkyl group having 1 to 1 carbon number] -18- 200936648 [Chemical 4]

[R3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. However, when two R3 are alkyl groups having 1 to 10 carbon atoms, they may be the same or different from each other. The polyoxyalkylene of the present invention is preferably one having 5 to 100 units (HSi03/2) per molecule, preferably 6 to 80, more preferably 7 to 60, and more preferably 8 to 40 people are particularly good. When the number of the unit (HSi03/2) units is too small, the cured polyoxymethane is likely to be deteriorated in heat resistance. On the other hand, when the number of the above units (HSi03/2) is too large, the polyoxyalkylene tends to be highly viscous and is difficult for the operator. The following three types are exemplified as the above-mentioned constituent unit (ii). The polyoxyalkylene of the present invention may contain only one type of constituent unit or two or three types. Further, when a plurality of constituent units are included, they may be the same or different from each other. (A) (A-(R1)#.- [In the formula, A is an organic group having a carbon-carbon unsaturated group having a carbon-carbon unsaturated group of 2 to 10, and R1 is a carbon number of 1 to 20 An alkyl group, a divalent aromatic group having 6 to 20 carbon atoms, or a divalent alicyclic group having 3 to 20 carbon atoms. η is 0 or 1]. -19- 200936648

Wherein A is an organic group having 2 to 10 carbon atoms having a carbon-carbon unsaturated group capable of hydrogenation, R 2 is an alkyl group having 1 to 10 carbon atoms, or a carbon-carbon having a hydrogenation reaction; An organic group having 2 to 10 carbon atoms in a saturated group. When R2 is an organic group having 2 to 10 carbon atoms which has a carbon-carbon unsaturated group which can be hydrogenated, the R2 and A may be the same or different from each other. 【化7】

A R3- and 01/2 R3 - wherein A is an organic group having a carbon number of from 10 to 10 having a carbon-carbon unsaturated group capable of hydrogenation, and R3 is an alkyl group having from 1 to 10 carbon atoms, or has An organic group having 2 to 10 carbon atoms of a carbon-carbon unsaturated group which can be hydrogenated. However, when two R3 are alkyl groups having a carbon number of 1 to 1 Å, the same r3 may be the same or different from each other. Further, when two R 3 are an organic group having 2 to 10 carbon atoms of a carbon-carbon unsaturated group capable of a gasification reaction, the R 3 and A may be the same or different from each other, or both may be the same. . Further, as the above-mentioned constituent unit (iii), the following two types are exemplified. The polyoxyalkylene of the present invention may contain only one type of constituent unit or two or three types. Moreover, when a plurality of constituent units are included, they may be the same or each other. 200936648 [Chem. 8]

[In the formula, R5 is an alkyl group having 1 to 6 carbon atoms]. 【化9】

[In the formula, R2 is a carbon number which may be the same or different from each other. The oxygen atom in the former constituent unit is the alkoxycarbonyl group in any of the constituent units exemplified in the examples i) and (ii). The alkoxy oxime having the polyoxyalkylene of the present invention is preferably a unit. Further, the alkoxy group in the polyoxyalkylene of the present invention preferably comprises 1 to 100% of the total of the constituent units (i), (ii) and (iii), preferably 2 to 30%, and preferably 3 4 to 10% is especially good. The ratio (number ratio) of the alkoxyfluorenyl group containing the isopropoxy methoxy group is preferably 50% or more, more preferably 70% or more. As described above, with the polyalkylene oxide of the present invention, the hardening workability of the polyoxyalkylene is good. Alkyl group - 21 - 1 to 10 alkyl group] The above-mentioned constituent unit (atomic bond formation, based on the number ratio from the above-mentioned precursor group, the number is based on -2 0 %, more preferably, thiol group In the case of isopropyl, the amount of the alkoxy fluorenyl group is too small at 60%, and the above effects are not sufficiently exhibited in 200936648. When the alkoxy fluorenyl group is too large, the polyoxyalkylene is likely to be deteriorated in stability. The polysiloxane of the invention may have a functional group other than the above-mentioned constituent units (i), (ii) and (iii). For example, it may have a stanol group, and may have a halogenation such as SiCl depending on the type of the raw material to be produced. The ratio of the total number of decyl alcohol groups and halogenated fluorenyl groups in the polyoxyalkylene is preferably 10% or less based on the total number of constituent units (i), (ii) and (iii). It is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. When the ratio of the decyl alcohol group or the halogenated fluorenyl group is too large, the polyoxyalkylene is likely to be deteriorated in stability. The polyoxyalkylene is preferably a polyoxyalkylene having a constituent unit represented by the following general formula (1). [化1 0]

Wherein A is an organic group having 2 to 10 carbon atoms of a carbon-carbon unsaturated group capable of hydrogenation, R1 is an alkylene group having 1 to 20 carbon atoms, and a divalent aromatic having 6 to 20 carbon atoms; a divalent alicyclic group having a carbon number of 3 to 20, η being 0 or 1 'R 2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon-carbon unsaturated group having a hydrogenation reaction. An organic group having 2 to 10 carbon atoms (R2 in one molecule may be the same or different), and R3 is a hydrogen atom or an organic group having 2 to 10 carbon atoms having a carbon-carbon unsaturated group capable of hydrogenation reaction, R4 Is a hydrogen atom, an alkyl group having a carbon number of 1 to 10, or an organic group having a carbon number of 2 to 10 having a carbon-carbon non--22-200936648 saturated group which can be hydrogenated (the R4 in 1 molecule may be the same or a phase Iso), R5 is a carbon number of l~6 alkyl 'v, x, y and z are positive numbers, w is 0 or a positive number, 0.001Sx/(v + w) > 0.01 ^y/ ( v + w )$2 , O.Ol^z/ ( v + w + x + y ) $1. However, when w = 〇., at least one of R2, R3 and R4 is an organic group having 2 to 10 carbon atoms which has a carbon-carbon unsaturated group which can be hydrogenated. In the above general formula (1), the ν' w, X, y, and z tables do not contain the number average ratio 値 of each constituent unit of the polyoxyl oxymethane molecule. v, x, y, and Z are positive numbers, and w is 0 or a positive number. In the above general formula (1), 'v is preferably 5 to 100, preferably 6 to 80, more preferably 7 to 60, and particularly preferably 8 to 40. In the above general formula (1), A is an organic group having 2 to 10 carbon atoms which has a carbon-carbon unsaturated bond capable of hydrogenation. The organic group A is not particularly limited as long as it has a carbon-carbon double bond or a bond functional group which can be hydrogenated. Specific examples thereof include a vinyl group, an o-styryl group, a methylstyrene fluorenyl group, a p-styryl group, an acryloyl group, a methacryl fluorenyl group, an acryloxy group, a methacryloxy group, and a 1- Propylene, 1-butenyl, 1-pentenyl, 3-methyl-1-butenyl, phenylvinyl, vinyl, 1-propenyl, 1-butenyl, 1-pentenyl , 3-methyl-1-butenyl, phenylbutenyl and the like. When the polysiloxane of the present invention contains two or more of the above-mentioned organic groups A, the organic groups A in one molecule may be the same or different from each other. As the organic group A, a raw material, a vinyl group having a small carbon number, and a p-styrene group having good reactivity are preferable. When the carbon number is small, the ratio of the polyoxyalkylene cured product to the inorganic component is large, which is related to the excellent heat resistance. -23- 200936648 In the above general formula (1), R1 is a stretching group (2-valent aliphatic group) having a carbon number of 1 to 20, a divalent aromatic group having a carbon number of 6 to 20, or a carbon number of 3 to 20 Valence alicyclic group. Examples of the alkylene group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an η-propyl group, an i-propyl group, an η-butylene group, a hydrazine-terminated butyl group and the like. Examples of the divalent aromatic group having 6 to 20 carbon atoms include a phenylene group and a naphthyl group. Further, examples of the divalent alicyclic group having 3 to 20 carbon atoms include a divalent hydrocarbon group having a norbornene skeleton, a tricyclodecane skeleton or an adamantane skeleton. Further, in the above general formula (1), η is 0 or 1. From the viewpoint of having a small carbon number and a high heat resistance of the polyfluorene oxide, η = 〇 is preferable. In the above general formula (1), w is preferably 0 to 40, more preferably 〇 30, and most preferably 〇 20, and particularly preferably 〇 10 . In the above general formula (1), R2 is a hydrogen atom, an alkyl group having 1 to 1 carbon atom, or an organic group having 2 to 10 carbon atoms which has a carbon-carbon unsaturated bond which can be hydrogenated. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group and the like. Any of these aliphatic groups and alicyclic groups may be either linear or branched. The organic group having 2 to 10 carbon atoms which has a carbon-carbon unsaturated bond capable of hydrogenation reaction may have a double bond or a bond functional group of a carbon-carbon which can be hydrogenated, and is not particularly limited. Examples of vinyl, o-styryl, methylstyryl, p-styryl, propylene fluorenyl, methacryl fluorenyl, acryloxy, methacryloxy, 1-propenyl, 1_ Butenyl, 1-pentenyl, 3-methyl-1-butenyl, phenylvinyl, vinyl, 1-propenyl, 1-butyr, 1-pentyl, 3-methyl Base_1_丁丁基, phenylbutyrate, and the like. R2 in one molecule may be the same species, or may be a combination of 2-24-200936648 or more. R2 is excellent in heat resistance with a small carbon number, and is particularly preferable in view of a hydrogen atom, a methyl group, and a hardening reaction which can be added to polyoxyalkylene. In the above general formula (1), X is 0.1 to 40 to 30', more preferably 0.2 to 20, particularly preferably 0.3 to 10, and in the above general formula (1), R3 is a carbon atom-carbon unsaturated bond of a hydrogen atom. The carbon-carbon unsaturated bond group having a carbon number of 2 to 10 is only a functional group having a double bond or a bond bond having a carbon, and no vinyl group, o-styryl group or meta-styrene is produced. Base, fluorenyl, methacryl fluorenyl, propylene methoxy, propylene, 1-butenyl, 1-pentenyl, 3-methyl-alkenyl, vinyl, 1-propenyl, 1- Butenyl, 1-butenyl, phenylbutenyl and the like. In one molecule, 〇 can be a combination of two or more different types. As the hardening reaction of R3, the carbon number is small, and the polyoxyalkylene is hardened. From the viewpoint of hydrogen atom and vinyl group, it is preferred. In the above general formula (1), R4 is a hydrogen atom group or an organic group having a carbon-carbon unsaturated state which can be hydrogenated. Specific examples of the alkyl group include a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a fluorene chain, a branched chain or a cyclic group. As the organic group having 2 to 10 carbon atoms which has a hydrazable unsaturated bond, it is only a polyoxyalkylene hardened vinyl group. Further, a hydrogen atom and a vinyl group are preferred, and preferably 〇. 1 〇 or a hydrazine-hydrogenated anti-base. The carbon which is a hydroquinone hydrogenation reaction is particularly limited, and examples thereof include a styryl group, a propenyl propylene oxy group, a 1-butenyl group, a phenylethyl group [-pentenyl group, and a 3-methyl group. R.3 may be the same species, or a carbon number of 2 to 10, methyl, ethyl, propyl, hydrazine, which may be an alkane and a bond having a carbon number of 1 to 10, which is excellent in heat resistance. The base or the like may be a carbon-carbon having a hydrogenation reaction of -25 to 200936648, a carbon-carbon double bond or a bond functional group, and may be exemplified as a styrene group or a methyl group. Styryl, p-styryl, propyl, methacryl fluorenyl, propylene methoxy, methacryloxy, b propylene, b butyl, 1-pentenyl, 3-methyl 1-butenyl, phenylethyl, vinyl, 1-propenyl, 1-butenyl, 1-pentenyl, 3-methyl-1-butenyl, phenylbutenyl Wait. R4 in one molecule may be the same species or may be a combination of two or more different species. As R4, a hydrogen atom, a methyl group and a vinyl group are preferred from the viewpoint of good reactivity or a small carbon number, and a methyl group is particularly preferable from the viewpoint of ease of handling of a raw material or an intermediate product. In the above general formula (1), y is preferably 〇·ΐ~50, more preferably 0.5 to 30, most preferably 1 to 20, and particularly preferably 2 to 10. In the above general formula (1), R5 is an alkyl group having 1 to 6 carbon atoms, and specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. In the above general formula (1), z is preferably from 0.1 to 20, more preferably from 0.2 to 10, most preferably from 0.3 to 8, and particularly preferably from 0.5 to 5. In the above general formula (1), a preferred relationship between v, w and X is 0.001 ^ x / ( v + w) $2, preferably 〇.〇l$x/(v + w) $1, more preferably 0.02Sx / ( v + w) S0.7 ' is particularly good for 〇.〇4^χ/ ( v + w) ^0.5 . When x/(v + w) is too small, the viscosity will change, and the heat resistance of the heat-hardened material without the catalyst tends to decrease. On the other hand, when x/( v + w ) is too large, the heat resistance of the heat-cured material without a catalyst tends to be lowered. The preferred relationship between v, w and y is 〇.〇1 Sy/ ( v + w) $2, preferably 〇.〇5Sy/(v + w) S1, more preferably 〇_lgy/(v + w) S0.7 200936648 'Special good is 0.15Sy/(v + w) $0_4. When y/(v + w) is too small, the viscosity is high, or the heat resistance of the heat-cured material without the catalyst tends to decrease. On the other hand, when y/(v + w) is too large, the heat resistance of the heating hardener under no catalyst tends to be lowered. Further, a preferred relationship between v, w, X, y and Z is 0.011$z/(v + w + x + y ) SI, preferably 0.02 ^ z/(v + w + x + y ) ^ 0.5 1 more preferably 0.0 3 ^ z/( v +w + x + y) ^ 0.3 > Particularly preferably 0 · 04 S z/(v +w + x + y) S 〇·1 0 . When z/(v + w + x + y) is too small, the heat hardenability under no catalyst tends to decrease. On the other hand, when z/(v + w + x + y) is too large, the storage stability of the polyxide chamber may be lowered, or the heat resistance of the heat-cured material may be lowered. However, when W=〇, R2 At least one of R3 and R4 is an organic group having 2 to 10 carbon atoms having a carbon-carbon unsaturated group capable of a sand-hydrogenation reaction. In the above general formula (1), V, W, X, y, and z are polyoxoxanes satisfying the above conditions, and have low viscosity and excellent workability, and the obtained cured product φ forms a film having a good appearance and is excellent in heat resistance. . The polyoxyalkylene of the present invention has a number average molecular weight of from 500 to 20,000. The number average molecular weight is preferably from 700 to 15,000, more preferably from 900 to 1,000,000, and particularly preferably from 1,000 to 5,000. By using a number average molecular weight by GPC (gel permeation chromatography), for example, as a column, GL-A130-S (porous micro-spherical polymer gel) manufactured by Hitachi Chemical Co., Ltd. It is obtained by using polystyrene as a standard substance. The polyoxyalkylene of the present invention is in the form of a liquid, 25. (The viscosity in the middle is -27-200936648 3 0000mPa_s or less, preferably 1 0000 mPa, s or less is preferred, and 5 00 m P a · s or less is better '300 00 m When P a · s or less, it is most preferable, and it is especially preferable when it is less than 100 mPa.s. However, the lower limit of the above-mentioned viscosity is generally 1 mPa·s. The method for producing polysiloxane of the present invention is to have three The hydrolysis-based ruthenium compound (T), the ruthenium compound (D) having two hydrolyzable groups, and the ruthenium compound (M) having one hydrolyzable group are hydrolyzed in the presence or absence of an organic solvent. In the second step of the condensation reaction, at least one of the above-mentioned oxime compound (T), the above ruthenium compound (D), and the above ruthenium compound (M) has an anthracene hydrogen group, and the above-mentioned ruthenium compound (T) and the above ruthenium compound ( D) and at least one of the above-mentioned ruthenium compound (M) having a carbon-carbon unsaturated group capable of hydrogenation reaction. Further, in the present invention, the aromatic hydrocarbon having a boiling point of 901 or more after the first step is provided. The second step of distilling off water in the presence of the solvent formed is preferred. The manufacturer of the polyoxyalkylene of the present invention The type, the amount of use, and the like of the ruthenium compound (T), the ruthenium compound (D), and the ruthenium compound (M) used in the first step are as described above. In the method for producing a polysiloxane of the present invention, ruthenium The hydrolyzable group of the compound (T) and the hydrazine compound (D) is an alkoxy group, and the hydrolyzable group of the hydrazine compound (M) is preferably an alkoxy group or a decyloxy group. a step of subjecting the hydrazine compounds (T), (D), and (M) to a hydrolysis/polycondensation reaction in the presence or absence of an organic solvent. Examples of the organic solvent include toluene, xylene 'benzene, and mesitylene. -28 - 200936648 An aromatic hydrocarbon such as ethylbenzene; an ether such as diisopropyl ether; an ester such as ethyl acetate or 2-methoxy-1-methylethyl acetate; etc. These compounds may be used alone or Further, the non-polar solvent such as the aromatic hydrocarbon may be used in combination with a polar solvent such as a lower alcohol such as methanol, ethanol or isopropyl alcohol. When the organic solvent is used in the first step, the use is carried out. Quantity, the total amount of bismuth compounds (T), (D) and (M) is taken as 100 mass The amount is preferably 0.5 to 10 parts by mass, more preferably 0.8 to 7 parts by mass, most preferably 1 to 5 parts by mass. As the reaction solvent, a boiling point of 90 such as toluene, xylene, mesitylene or ethylbenzene is used. The method of aromatic hydrocarbons above °C is preferred in the first step of producing a polyoxyalkylene and in the step of distilling off volatile components, thereby suppressing the generation of gel. In the first step, as an organic solvent When a nonpolar solvent such as toluene or xylene is used, it may preferably be used together with a lower alcohol such as methanol, ethanol or isopropyl alcohol or another polar solvent. The above nonpolar solvent and lower alcohol or other polar solvent may be used. When used, the reaction solution can be made uniform, so that the reaction enthalpy can proceed smoothly. Further, the lower alcohol is bonded to the ruthenium atom to form an alkoxy group. For example, when an isopropyl alcohol is used, a polyoxyalkylene group having a good balance of stability and reactivity can be obtained by introducing an isopropoxy fluorenyl group into a polyoxyalkylene. In the above first step, the amount of water to be added is preferably 0.5 to 5 moles per mole of the hydrolyzable group, and preferably 1 to 2 moles. Further, the hydrolysis of the ruthenium compounds (T), (D) and (M). The polycondensation reaction can be carried out without a catalyst or under a catalyst. When a catalyst is used, an inorganic acid such as sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid; an acid catalyst exemplified as an organic acid such as formic acid, acetic acid, oxalic acid or p-toluenesulfonic acid can be generally used. When an alkaline catalyst is used, -29-200936648 'Because the hydrogen group is hydrolyzed to generate hydrogen gas, it is preferably not used. When water is added using an acid catalyst or without a catalyst, the mixture is stirred at room temperature to hydrolyze. The polycondensation reaction can be easily carried out. It can be heated or cooled as necessary. However, when the _gastric 丨# is carried out without a catalyst, it is preferred that at least one of the ruthenium compounds (T), (D) and (M) is an acid sand compound which is produced by a hydrolysis reaction. The generated acid acts as a catalyst. Further, the above ruthenium compounds (T), (D) and (M) are hydrolyzed.

When the reaction does not produce an acid compound, the hydrolysis/polycondensation reaction can be carried out rapidly by using an acid catalyst, which is preferable. The amount of the acid catalyst used is equivalent to 0.01 to 20 moles for the total amount of the ruthenium atom in the ruthenium compound (T), the sand atom in the ruthenium compound (d), and the ruthenium atom in the ruthenium compound (M). The amount of % is preferably equal to the amount of 〇1 to 10 mol%. The hydrolysis of the first step described above and the completion of the polycondensation reaction can be known, for example, by analyzing the reaction solution by gas chromatography (GC).

When only the ruthenium monomer (Ml) is used as the ruthenium compound (M), the GC peaks of all the sand compounds (T), (D) and ruthenium monomer (Ml) disappear.

Further, the end of the reaction can be confirmed. When only the sand dimer (M2) is used as the ruthenium compound (M), the GC peak of the ruthenium compounds (T) and (D) disappears and the peak size of the ruthenium dimer (M2) almost stops. Confirm the end of the reaction. When the ruthenium compound (M) is used as a ruthenium monomer (Ml) and a ruthenium dimer (M2), the GC peaks of the ruthenium compounds (T), (D) and ruthenium monomers (Ml) disappear and 矽The change in the peak size of the polymer (M2) almost stopped to confirm the end of the reaction. In the present invention, the second step of distilling off the water contained in the reaction liquid obtained in the first step in the presence of a solvent having an aromatic hydrocarbon having a boiling point of 90 ° C or more may be provided. This step is effective when the reaction in the above first step is carried out in the presence of an organic solvent. Thereby, the generation of gel can be suppressed. Further, as the solvent, toluene, xylene or the like is preferred. In the second step, the vacuum distillation is generally carried out, and in addition to the organic solvent or water, when the free alcohol is present, only the volatile components such as unreacted rhodium dimer (〇M2) are distilled off to obtain the desired polyfluorene. As the oxane, a polyoxyalkylene having a carbon-carbon unsaturated group, an anthracene hydrogen group and an alkoxyfluorenyl group which can be hydrogenated, and having a number average molecular weight of 500 to 20,000 can be obtained. In the method for producing a polyoxyalkylene of the present invention, it is preferred to obtain a polyoxyalkylene having a structural unit represented by the following general formula (2). [1 1 R2 , Si〇2/2 ^H-Si03/2j ^A-(RVSi〇3/2j (rS〇m^\ (2) R4 /y\ /z 〇 [where A is An organic group having 2 to 10 carbon atoms of a carbon-carbon unsaturated group of the hydrogenation reaction, and R1 is an alkylene group having 1 to 20 carbon atoms, a divalent aromatic group having 6 to 20 carbon atoms, or a carbon number of 3 to 20 a divalent alicyclic group, η is 0 or 1, R 2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an organic group having 2 to 10 carbon atoms having a carbon-carbon unsaturated group capable of hydrogenation reaction (R2 in one molecule may be the same or different), and R3 is a hydrogen atom or an organic group having a carbon number of 2 to 10 having a carbon-carbon unsaturated group capable of hydrogenation, and R4 is a hydrogen atom and a carbon number of 1 to 1〇的院基, or a carbon-carbon non-31 - 200936648 saturated carbon group having a carbon number of 2 to 10 (the r4 in one molecule may be the same or different), and the ruler 5 is carbon Number 1 to 6 alkyl, ;^,)^, 5^ and 2 are positive numbers, w is 0 or a positive number '0.001$x/(v + w) > 0.01 ^ y/ ( v + w )> .Ol^z/ ( v + w + x + y ) SI. However, when w=〇, at least one of R2, R3 and R4 is a carbon having a carbon-carbon unsaturated group capable of hydrogenation reaction. 2 to 10 organic groups. A, R1, η, R2, R3, r4, r5, v, w, χ, 丫 and redundancy are preferably the same as those described in the above general formula (i). When the polysiloxane of the constituent unit represented by the formula (2) is used, the ratio of the amounts of the ruthenium compounds (T), (D) and (M) used in the first step is 100 mol%. Preferably, each is 30 to 80 mol%, 1 to 30 mol%, and 5 to 50 mol%, more preferably 40 to 75 mol%, 2 to 25 mol%, and 10 to 45 mol%, It is particularly preferably 50 to 70% by mole, 2 to 2, 0% by mole, and 1 to 5 to 4% by mole. The manufacturing method of the present invention will be described in detail below by way of example. For the structural unit T (HSi03/ 2) Unit, as structural unit D, contains (H ( Me ) Si02 / 2 ) units, as a structural unit Μ contains (Vi ( Me ) 2Si01/2 ) units, as alkoxy groups (iPr01/2) units and (Et 〇 1/2) The method for producing a polyoxyalkylene unit is described. Further, "Me" represents a methyl group, "Et" represents an ethyl group, "ipr" represents an isopropyl group, and "Vi" represents a vinyl group. Structure list The compound of the general formula (3) of the (HSi03/2) unit of the position T can be used. -32- 200936648 [Chemical 1 2] X1 H-Si-X1 (3) [wherein 'X1' represents an alkoxy group having 1 to 1 carbon atoms, a hydrolyzed member such as a halogen atom, or a lysate- 3⁄43. The plural X1 may be the same or different in the same molecule. In the above general formula (3), the methoxy group is derived from a methoxy group, an ethoxy group, a propoxy group, and the like. A chlorine atom or the like is preferred. Specific examples of the compound represented by the above formula (3) include trimethoxydecane, triethoxysilane, tripropoxydecane, and trichlorodecane. These can be used individually or in combination of 2 or more types. As the oxime compound (D) forming the unit of the structural unit D (H (Me) Si 〇 2, 2), the compound represented by the following general formula (4) can be used. [Chemical Formula 1] Ο Η X2-Si-X2 (4) ch3 [wherein, X2 represents an alkoxy group having 1 to 10 carbon atoms, a hydrolyzable group such as a halogen atom, or a hydroxyl group. The plural X2 may be the same or different in the same molecule. In the above general formula (4), X2 is preferably a methoxy group, an ethoxy group, a propoxy group, a chlorine atom or the like from the viewpoints of ease of availability of raw materials, good reactivity, and the like. -33- 200936648 Specific examples of the compound represented by the above general formula (4) include dimethoxymethyl decane, diethoxymethyl decane, dipropoxymethyl fluorene, and dichloromethyl. Decane and so on. These may be used alone or in combination of two or more. As the ruthenium compound (M) which forms a unit of the structure (VMMehSiOm), a ruthenium dimer (M2) represented by the following formula (5) (1,3-diethylenetetramethyldioxane) can be used. Or a fluorene monomer (Ml) represented by the following general formula (6).

[In the formula, X3 represents an alkoxy group having 1 to 10 carbon atoms, a hydrolyzable group such as a halogen atom or a hydroxyl group]. In the above general formula (6), X3 is preferably a methoxy group, an ethoxy group, a propoxy group, a chlorine atom or the like as described in the above general formula (6) from the viewpoints of ease of availability of raw materials, good reactivity, and the like. Specific examples of the compound include methoxyethylene dimethyl decane, ethoxyethylene dimethyl decane, propoxy ethylene dimethyl decane, and vinyl chloride dimethyl decane. These can be used singly or in combination of two or more. -34- ❹

200936648 As described above, when the ruthenium compound (M2) is used as the ruthenium compound (M2), the ratio of the residue to the other raw materials is increased, for example, it must be 1 times the mass. When the ruthenium dimer (M2) is used in this way, it is necessary to use a monomer (Ml) which is more expensive than the general one, and it is a practical raw material at a cheaper price. For example, as the above ruthenium compound (T), D) and (Μ), when triethoxy decane, dimethoxymethyl decane, and 1,3-divinyl fluorene dioxane are used, the polyoxy siloxane can be produced as follows.

These hydrazine compounds and an organic solvent such as xylene are placed in a reaction, and the inside of the reactor is replaced with nitrogen or the like to form an inert environment. Then, the reaction mixture is mixed with an acid catalyst such as an aqueous hydrochloric acid solution to carry out a water condensation reaction (first step). The temperature of the reaction system is generally 〇°c-. In the first step, a lower alcohol such as isopropyl alcohol may be used as a method for using the lower alcohol, and the reactor or the P medium may be dropped in advance. Thereafter, the water and the organic solvent are dissolved in the reaction liquid using a distiller or the like to separate the polyoxyalkylene (second step). The polyoxyalkylene of the present invention has a crosslinked structure by hydrogenation reaction of a carbon-carbon unsaturated group contained in a hydrogenation reaction of one polyoxyalkylene with a polyfluoreneoxyalkyl group. Polyoxane. In the production of the polyoxyalkylene cured product, as described later, a catalyst for hydrogenation reaction can be used. The curing temperature when the catalyst for the hydrogenation reaction is not used, 5): Therefore, 2~3: Residual amount: to, each of the methyl groups: in the middle of the apparatus, while stirring, poly-8 0 °C class.丨 触 丨 丨 丨 . 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : In the temperature of this range, the fixed hardening temperature, or a combination of temperature rise and/or temperature drop can be combined. Further, the hardening time is generally 〇·1 to 10 hours. In the present invention, the method for producing a polysoda oxide cured product is characterized in that, in the non-existence of the above-mentioned polyoxoxane of the present invention in the presence of a catalyst for hydrogenation reaction, it is heated at a temperature of 150 ° C or higher and 70 (TC or lower). The step is characterized in that, in the temperature of the range, the curing temperature can be fixed, or the combined temperature rise and/or temperature can be lowered. Further, the hardening time is generally 〇1 to 1 〇 hour, preferably 0.5 to 5 hours, and from room temperature to The heating condition of the temperature in the above range is not particularly limited. When the curing is carried out at the temperature in the above range, the alkoxyfluorenyl group in the polyoxyalkylene is also reacted to give crosslinking, and the obtained polyoxyalkylene cured product is obtained. It is essentially an alkoxy-free fluorenyl group, which is excellent in heat resistance. It is presumed that under the condition of no catalyst, the hydrogenation reaction rate is not significantly large, and in the initial stage of the reaction, the molecule of the polyoxane can also be a certain The degree of free movement 'make the reaction of the alkoxy fluorenyl group less hindered. The other method for producing the polyoxymethane cured product of the present invention' is to hydrogenate the above polyfluorene oxide of the present invention in the hydrazine. With the non-existence of the catalyst, to 5 0 r or more, the step of heating at a temperature of not less than 150 ° C, and the step of heating at a temperature of 1 5 〇 ° C or higher. (The following steps include heating in the order of the temperature. 50. (: The above is less than 150 Temperature range of °C, and temperature range of 150 °c or more and 700 °C or less 'fixable hardening temperature, or combined temperature rise and/or temperature drop. 5 (TC above 150 〇C in temperature) The reaction of the oxy group with the base 200936648 (hydrolysis/polycondensation reaction) partially hardens to form a crosslinked structure, and thereafter, crosslinking is carried out mainly by a hydrogenation reaction at a temperature of from 150 ° C to 700 ° C. When the decane group contains a stanol group, crosslinking is imparted by a condensation reaction at a relatively low temperature. As an advantage of partially curing, the degree of freedom in the operation of forming a polyoxyalkylene cured film of a substrate described later can be improved. For example, a coating film of polyoxyalkylene is formed on the surface of a plate-like substrate, and is heated to a temperature of not more than 50 ° C and less than 150 ° C to harden a part of the polyoxoxane coating film, thereby losing the polyoxyalkylene oxide. Fluidity, processing the laminate as necessary (with polyoxyalkylene oxide) The plate-shaped base material of the partially hardened film is formed into a desired shape. Thereafter, the laminate is heated to a temperature of 150 ° C or more and 700 ° C or less, and the hardened film is partially cured by completely curing the polyoxymethane. A composite of a uniform polyoxyalkylene hardened film is formed on the surface of the plate-like substrate. Not only the above-mentioned plate-like substrate but also a substrate having a complicated shape may form a hardened film. © Also, as another example, in a particulate form A coating film of polyoxyalkylene is formed on the surface of the material, heated to a temperature of 50 ° C or more and less than 150 ° C, and a part of the polyoxyalkylene coating film is hardened to obtain a coated particle having a hardened film of a polyoxymethane. Thereafter, the coated particles are heated to a temperature of 150 t or more and 70 (TC or less), and a part of the hardened film of the polyoxyalkylene can be completely cured to form a composite of a uniform polyoxyalkylene hardened film on the surface of the particulate substrate. particle. The hardening time of a part of the hardened part is less than 50 ° C and less than 150 ° C, generally 〇. 1~1 〇 hours, preferably 5 5 5 hours. -37- 200936648 The hardening time after complete hardening at a temperature of 150 ° C or more and 700 ° C or less is generally 〇. 1~1 〇 hours, 〇. 5~5 hours is preferred. When the catalyst for the hydrogenation reaction is used, it can be hardened at a lower temperature (e.g., room temperature ~ 150 ° C, preferably 50 ° C to 150 ° C). However, the obtained polyoxymethane cured product tends to be an unreacted alkoxy fluorenyl group, and when the cured product is further heated at a high temperature (for example, 600 ° C or higher), a volatile component such as an alcohol is generated. The reason why the unreacted alkoxy fluorenyl group is likely to remain is presumed to be that the crosslinking by the hydrogenation reaction proceeds rapidly, so that the movement of molecules of the copolyoxane is limited to a short period of time, and the alkoxy group is restricted. The thiol is blocked and loses its chance of reaction. The hardening time when using the catalyst for the hydrogenation reaction is generally 〇5 to 2 4 hours, preferably 0.1 to 5 hours. Examples of the catalyst for the rhodium hydrogenation reaction include monomers, organometallic complexes, metal salts, and metals selected from metals of Groups 8 to 10 such as cobalt, nickel, rhodium, ruthenium, palladium, rhodium, and uranium. Oxide, etc. Platinum-based catalysts are generally used. The platinum-based catalyst may, for example, be a cis-PtCh ( PhCN ) 2 , a uranium carbon or a ruthenium 1,3-diethylene tetramethyldioxane coordinated by a lead complex (Pt ( dvs ) ), Platinum methyl cyclic oxime complex, platinum carbonyl-vinyl methyl cyclic oxime complex, bis(diphenyleneacetone) dilead, chloroplatinic acid, bis(ethylene) four Chloroplatinum, cyclooctadiene dichloroplatinum, bis(cyclooctadiene)platinum, bis(dimethylphenylphosphine)dichlorolead, ruthenium (triphenylphosphine)platinum, and the like. Among them, a platinum complex (Pt(dvs)) coordinated with 1,3-diethylenetetramethyldioxane, a platinum vinyl methyl azepine complex, a cobalt carbonyl, an ethylene Methyl cyclic alkane complex. And, Ph represents a phenyl group.触-38- 200936648 The amount of the medium used is preferably from 1 ppm by mass to 1000 ppm by mass, preferably from 0.5 to 100 ppm by mass, and more preferably from 1 to 10 ppm by mass. good. When a catalyst for hydrogenation reaction is used, it is possible to add a ruthenium hydrogenation reaction inhibitor in order to increase the gelation inhibition and storage stability of the catalyst-added polysiloxane. Examples of the hydrazine hydrogenation reaction inhibitor include a methyl vinylcyclotetraoxane, an acetylene alcohol, a decane-modified acetylene alcohol, a hydrogen peroxide Q, a nitrogen atom, a sulfur atom or a phosphorus atom. Hydrogenation reaction inhibitors and the like. The hardening of the polyoxyalkylene is independent of the presence or absence of the catalyst, and can be carried out in the air or in an inert gas atmosphere such as nitrogen. However, in the case where an alkoxyfluorenyl group is present in the polyoxyalkylene oxide, an environment containing water in an alkoxythio group hydrolyzable reaction is preferred. In the air alone, the alkoxy fluorenyl group contains water to the extent that it can be hydrolyzed, so that it can be sufficiently hardened. The other method for producing the polyoxymethane cured product of the present invention is a preferred method in which the front stage is hardened in the air, and the latter stage is hardened in the air or in an inert gas atmosphere. The polysiloxane of the present invention is a liquid material having a viscosity of 30,000 mPa*s or less at 25 ° C as described above, so that it can be directly coated on the surface of the substrate, but may be diluted with a solvent if necessary. . When a solvent is used, a solvent for dissolving polysiloxane is preferable, and examples thereof include an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a chlorinated hydrocarbon solvent, an alcohol solvent, an ether solvent, a guanamine solvent, and a ketone. Various organic solvents such as a solvent, an ester solvent, and a 2-methoxyethanol solvent. When a solvent is used, it is preferred to carry out a heating step of hardening the polyoxyalkylene to volatilize the solvent contained in the coated film. Solvent volatilization can be carried out in air at -39- 200936648 or in an inert atmosphere. Heating may be carried out by evaporating the solvent, but the heating temperature at this time is preferably less than 150 ° C, and preferably less than 150 ° C at 50 ° C or higher. In another method for producing a polyoxyalkylene cured product of the present invention, the polyoxyalkylene oxide is heated at 5.0 ° C or higher and less than 150 ° C to partially cure it, and this may be used as a solvent volatilization step. The polyoxyalkylene of the present invention is provided for hardening, and various additives can be added. Examples of the additive include reactive thin-release agents such as tetraalkoxy decane and trialkoxy decane (trialkoxy decane, trialkoxyvinyl decane, etc.). These additives are used insofar as the obtained polyoxyalkylene cured product does not impair heat resistance. For the coating of the polyoxyalkylene group, a general coating method such as a casting method, a spin coating method, or a bar coating method can be used. The substrate which can form a film of a polyoxyalkylene cured product can be used only as a structure having a material and a shape which can form a coating film by coating. However, when a substrate having low heat resistance is used, the upper limit of the curing temperature of the polyoxyalkylene is the temperature at which the substrate is resistant.构成 The constituent materials of the substrate are generally inorganic materials, organic materials, or materials of these combinations. Preferred examples of the material include metals, alloys, ceramics, wood, and plastics. Further, examples of the shape thereof include a sheet, a plate, a cube, a rectangular parallelepiped, a pyramid, a cone, a linear body (straight line, a curve, etc.), an annular body (circular shape, a polygonal shape, etc.), a tube, a ball, and the like. An amorphous body having irregularities, grooves, through holes, corners, and the like. Specific examples include sheet glass, tantalum wafers, processed plastics of various shapes, building materials, and various shapes of processed metals. -40- 200936648 The heat resistance of the polyoxyalkylene cured product can be measured by a differential thermal mass simultaneous measuring device (TG/DTA) or the like. The polyoxyalkylene oxide of the present invention is cured by a hardening agent which is not subjected to a catalyst for hydrogenation, and does not depend on the hardening conditions, and can reduce the temperature by 5% by weight to 1 000 ° C or more. It shows high heat resistance. [Embodiment] Q [Examples] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Example 1 A magnetic gas returning rotor, a titration funnel, a reflux condenser and a thermometer were placed in a 100 ml four-necked flask, and the inside of the flask was replaced with nitrogen. The reaction relay continues to flow into the nitrogen. 59.14g (3 60mmol) of triethoxy decane, 17.79g (120mm〇l) of trimethoxyvinyl decane, 6.92g (5 7.6mmol) of dimethoxy dimethyl decane, 1,1,3,3 - Tetramethyl oxalate 16.12 g (l20 mmol), 2-propanol 88.3 8 g and xylene 265.1 4 g were placed in a flask. Thereafter, a mixture of _28% hydrochloric acid 34-96 g and 2-propanol 44.19 g was slowly added from a titration funnel to the above mixture at room temperature (19 ° C). The temperature in the flask was maintained at 19 ° C to 22 during the dropping. ( Range of: After the dropwise addition of the mixture of hydrochloric acid and 2-propanol, the reaction solution is allowed to stand at room temperature -41 - 200936648 for 18 hours. Next, the volatile component containing water is reduced by the reaction liquid. The mixture was subjected to distillation (temperature: 23 ° C to 60 ° C, pressure: 52 to 1 mmHg) to obtain 42.79 g of a slightly pale yellow liquid (hereinafter referred to as "polyoxyalkylene (PI)"). (P1), the result of measuring the number average molecular weight (?η) by GPC was 1,300. Further, the viscosity at 25 °C was measured by a Ε-type viscometer to be 4 3 m P a · s. The loading amount of the ruthenium compound (mol ratio) and the above physical properties. @ Further, the analysis results of 1H-NMR (nuclear magnetic resonance spectroscopy) of polyoxy siloxane (P1) are as follows: • H-NMR (C6D6, 5 ( Ppm ) ) : - 0 · 2 ～ 0 6 ( br, S i - C H3 ), 0.9 ～ 1.5 (br, OCH(CH3) 2, 〇CH2CH3), 3.5~4.1 (br, OCH2CH3), 4 · 1 〜 5.5 ( br, O CH ( CH 3 ) 2, Si-H ), 5.7 to 6.4 (br, CH=CH 2 ). Reaction by W-NMR ' 1,1,3,3-tetramethyldioxane The rate is 55%. The reaction rate is obtained by the following. 0 First, borrow The ratio of the methyl group to the vinyl group bound to the ruthenium atom was determined by iH-NMR. The methyl group bonded to the sand atom was present from the dimethoxy dimethyl sand chamber and the 1,1,3,3 -tetramethyl group. In the case of aerobics, the vinyl group is derived from trimethoxyvinyl decane. Among them, trimethoxyvinyl decane and dimethoxy dimethyl decane are introduced into the polyoxane almost in a stoichiometric manner. The ratio from the ratio of the methyl group bound to the ruthenium atom to the dimethoxy dimethyl decane is the ratio from 1,1,3,3-tetramethyldioxane. In the alkane (P1), the ratio of unreacted or formed alkoxy-42-200936648 thiol (isopropoxy fluorenyl and ethoxylated) oxy groups is also observed by 1 H-NMR. Got it. Shown. Table 3 shows the numbers contained in one molecule per polyoxyalkylene from the Μη described in Table 1 and the ear ratios shown in Table 2. Next, using the obtained polyoxyalkylene, the polyoxyalkylene cured product was subjected to heat resistance and the above-mentioned polyoxyalkylene (the glass plate was coated without coating) with heat resistance and adhesion. 3 to a cured product (hardened film) with a film thickness of about ιμιη at 30 ° C. It has not been confirmed. The cured product was evaluated by the TG/DTA220, a differential thermal and thermal weight measuring device of the Seiko Electronics Co., Ltd., and the result was a nitrogen atmosphere. (The temperature at which the heating rate is reduced by 5% by weight is 1 000 °C or more, and the weight loss by 〇 is 4.3%. In the air environment (the temperature is reduced by 5% by weight, the temperature is 1 000 ° C or more. Also, by 1 3 Heating at 0 °C for 4 hours causes the infrared absorption of the hardened material (a portion of the cured product) to remain unreacted. The portion of the cured product consumes vinyl by hydrazine hydrogenation in the warm phase, followed by 1 30 ° C is hydrolyzed under conditions of 4 hours of heating, and can be adsorbed by an adsorbent, heated, desorbed, and low-temperature. Alkoxyfluorenyl group (Alkane analysis, such as the average two types of hardening conditions of each constituent unit of Table 2) Assessment of sexuality The medium is heat-hardened in an hour, and the fracture at this time is produced and the product of the company ("type name" is 20 ° C / min) is reduced by 1000 ° C. The speed of the hardened material is 20 ° C / min). The spectral results in the state, the heating of the vinyl TG/DTA shows a higher heat resistance, the alkoxy fluorenyl concentration-gas chromatography / -43- 200936648 mass analysis (TCT-GC/MS) It was confirmed that isopropyl alcohols and ethyl alcohols were detected, and a portion of the cured product heated at 130 ° C for 4 hours was heated to 400 ° C at a temperature increase rate of 20 ° C / min to obtain a cured product. There is no mass reduction. In addition, as a result of infrared absorption analysis (IR), it is confirmed that the hardened substance contains almost no vinyl group (that is, almost complete hydrogenation reaction). In the IR spectrum, the vinyl group is observed around lWOcnT1 and ΙόΟΟίίΐϊΓ1. Sexual absorption. The temperature of the hardened material reduced by 5% by weight of TG/DTA is above 1 °C in any of the nitrogen atmosphere and the air environment. The above polyoxyalkylene is used by bar coating (not Contains ruthenium hydrogenation catalyst) on steel sheet (SPCC After coating on -SD), it is heated at 130 ° C for 4 hours, and then heated at 170 ° C for 4 hours or at 200 ° C for 1 hour to be cured to obtain a cured product having a film thickness of about 1 μm. The film was not confirmed to have a fracture at this time. The hydrazine hydrogenation reaction by the above heat curing was confirmed by IR spectroscopy. For the obtained cured film, a square lattice peeling test was performed (in 8.7.1 and 8.5.2 of JIS Κ 5400). The adhesion of the steel plate is evaluated, and the good adhesion of 1 00/1 00 is confirmed. The above evaluation results are shown in Table 4. Example 2 44.35 g (270 mmol) of triethoxy oxime, 13.34 g (90 mmol) of trimethoxyvinyl decane, 2.16 g (18 mmol) of dimethoxy dimethyl decane, 1,1,3,3 - In the same manner as in Example 1, except that 12.09 g (90 mmol) of tetramethyl oxalate, 95.07 g of 2-propanol, 190.14 g of xylene, and 22.01 g of 1.28% hydrochloric acid were obtained, a slightly pale yellow liquid was obtained (hereinafter referred to as "Ju Chi Oxygen Institute (P2)") 31.i〇g. The result of measuring the Μη of the polyoxyalkylene (p2) was 11 Å. Further, the result of measuring the viscosity in 25t: was 34 mPa, s (refer to Table 1). Further, the results of 1H-NMR analysis of polyoxyxane (P2) are as follows: 〇iH-NMR (C6D6, 5 (ppm)): - 〇· 2 to 0.6 (br, S i - C Η 3 0 ), 0.9 to 15 (br, 〇CH(CH3)2, 〇CH2CH3), 3.5 to 4.1 (br, 〇CH2CH3), 4.1 to 5.5 (br, OCH (CH3) 2, Si-H), 5.7 to 6.4 (br, CH=CH2) ° The reaction rate of 1,1,3,3-tetramethyldioxane by 1H-NMR was 640/〇. Further, in the polyoxyalkylene (P2), an alkoxythio group (isopropoxy fluorenyl group and ethoxy fluorenyl group) which was not reacted or formed was observed. These analyses are shown in Table 2. Μ The molar ratio of each of the constituent units shown in Table 1 and Table 2, and the average number of constituent units contained in one molecule per polysiloxane, are shown in Table 3. Further, in the same manner as in Example 1, the heat resistance was evaluated by TG/DTA. The results are shown in Table 4. Example 3 49.28 g (300 mmol) of triethoxymethane, 12.60 g (85 mxnol) of trimethoxyvinyl decane, 3.36 g (15 mm 〇l) of trimethoxy(4-vinylphenyl)phosphonium-45-200936648, Dimethoxy dimethyl decane $ 77g ( 48mm 〇l) , 1,1,3,3-tetramethyl dioxane i 〇 75 g (8 〇 min 〇 1), 2-propanol 〇 5.69 g In the same manner as in Example 1, except that 2 to 38 g of toluene 2 U 38 g and 128% hydrochloric acid were used, 4292 g of a slightly pale yellow liquid (hereinafter referred to as "polyoxane (P3)") was obtained. The result of measuring Μη of the polyoxyalkylene (p3) was 1,200. Further, the result of measuring the viscosity in 25 Å was 93 mPa·s (refer to Table 1). 1 The analysis result of 1h_NMR of 'Jinsha Institute (P3) is as follows: 'H-NMR (C6D6,5 (ppm)): -0.2 to 0·6 (br,Si-CH3), 09 to 1.5 (br , 〇CH (CH3) 2, 〇CH2CH3), 3.5 to 4.1 (br, 〇CH2CH3), 4.1 to 5.4 (br'OCH (CH3) 2, Si-H), 5.5 to 6.7 (br, CH = CH2), 7.1 to 8.0 (br, aromatic proton) The reaction rate of 1,1,3,3-tetramethyldioxane by 1H-NMR was 64%. Further, in the polyoxyalkylene (P3), an alkoxy sand group (isopropoxy sand group and ethoxy sand group) which was not reacted or formed was observed. These analyses are shown in Table 2. The 莫η described in Table 1 and the molar ratio of each constituent unit shown in Table 2 were determined and found in Table 3 as the average number of constituent units included in one molecule of polyoxyalkylene. Further, in the same manner as in Example 1, the heat resistance was evaluated by TG/DTA. The results are shown in Table 4. -46 - 200936648 Example 4 Using 65.71 g (400 mmol) of diethoxy sand, 5.10 g (48 mmol) of dimethoxymethyl decane, and 1 8.64 g of iota, 3-divinyltetramethyldioxane ( A slightly pale yellow liquid (hereinafter referred to as "polyoxyalkylene (P4)") was obtained in the same manner as in Example 1 except that 1 OO mmol), 2-propanol ii 6.61 g, xylene 233.22 g, and 1.28% hydrochloric acid 25.48 g. 32.19g. The result of measuring the Μη of the polyoxyalkylene (P4) was 1,800. Further, the result of measuring the viscosity at 25 ° C was 549 mPa·s (refer to Table 1) ^ Further, the analysis result of 1H-NMR of polyoxyalkylene (P4) was as follows 〇W-NMR (C6D6, S ( Ppm ) ) : -〇· 1 ~〇·6 ( br,Si-CH3 ), 0.9 to 1.5 (br, OCH(CH3) 2, OCH2CH3), 3.5 to 4.1 (br, OCH2CH3), 4.1 to 5.4 (br, OCH (CH3) 2, Si-H), 5.65 to 6.4 (br, CH = CH2). The reaction rate of 1,3-diethylenetetramethyldioxane by 1H-NMR was 40%. Further, in the polyoxyalkylene (P4), unreacted or formed alkoxythiol groups were observed ( Isopropoxy fluorenyl and ethoxylated fluorenyl). These analyses are shown in Table 2. The molar ratio of each of the constituent units described in Table 1 and Table 2 is determined by the average number of each constituent unit contained in one molecule of polyoxymethane, and is shown in Table 3. Further, in the same manner as in the first embodiment, the heat resistance was evaluated by TG/DTA from -47 to 200936648. The results are shown in Table 4. Example 5 - 52.57 g (320 mmol) of ethoxy sand yard, 8_50 g (80 mmol) of dimethoxymethyl sand, and 14.91 g (80 mm〇i) of 1,3-diethylenetetramethyl dioxin. In the same manner as in Example 丨, a slightly yellowish liquid was obtained in the same manner as in Example 2, except that 2-propanol (1,5 g), xylene (2,2,5,5 g, and 1.28% of hydrochloric acid, 21,90 g) (hereinafter referred to as "polyoxyl (P5)". ") 28.28g. The result of measuring Μπ of the polysoda (P5) was 18 〇〇. Also, it was measured at 25. The result of the viscosity in 〇 was l95 mPa.s (refer to Table 1). Further, the results of 1H-NMR analysis of polyoxyalkylene (P5) are as follows: 〇iH-NMR (C6D6, 5 (ppm)): -0.1 to 〇6 (br, Si-CH3), 〇·9 to 1.5 (br, OCH (CH3) 2, 〇CH2CH3), 3.5 to 4.1 (br, OCH2CH3), 4 · 1 to 5 · 4 (br, OCΗ (CΗ3) 2, Si-H), 5.65 to 6.4 (br, CH = CH2 ). The reaction rate of 1,3-diethylenetetramethyldioxane by 1H-NMR was 3 8%. Further, in the polyoxyalkylene (P5), an unreacted or formed alkoxy sand group (isopropoxy sand group and ethoxy sand group) was observed. These analyses are shown in Table 2. The molar ratio of each of the constituent units described in Table 1 and Table 2 is determined by the average number of each constituent unit contained in one molecule of polyoxymethane, and is shown in Table 3. -48-200936648 Further, in the same manner as in Example 1, the heat resistance was evaluated by TG/DTA. The results are shown in Table 4. Example 6 46.00 g (280 mmol), dimethoxymethyl decane 11.15 g (105 mmol), 1,3-diethylenetetramethyldioxane 13.05 g (70 mmol), 2- using diethoxy chopping In the same manner as in Example 1, except that 94.92 g of propanol, i89_84 g of xylene, and 0.44 g of 0. 28% hydrochloric acid were used, a slightly pale yellow liquid (hereinafter referred to as "polyoxyalkylene (P6)") was obtained. . The result of measuring the Μη of the polyoxyalkylene (P6) was 1,500. Further, the result of measuring the viscosity at 25 ° C was 6 7 mPa · s (refer to Table 1). Further, the results of 1H-NMR analysis of polyoxyalkylene (P6) are as follows: 〇^-NMR (C6D6, 5 (ppm)): - 0.1 〜0 ' 6 (br, S i - C Η 3 ), 0.9 ~1.5 (br, OCH (CH3) 2, OCH2CH3), 3.5 to 4.1 〇 (br, OCH2CH3), 4.1 to 5.4 (br, OCH (CH 3 ) 2, Si-H), 5·65 to 6.4 (br, CH = CH2). The reaction rate of 1,3-diethylenetetramethyldioxane by 1H-NMR was 47%. Further, in the polyoxyalkylene (P6), an alkoxycarbonyl group (isopropoxy fluorenyl group and ethoxy fluorenyl group) which was not reacted or formed was observed. These analyses are shown in Table 2. The 莫η described in Table 1 and the molar ratio of each constituent unit shown in Table 2, the average number of each constituent unit contained in one molecule of polyoxymethane was -49-200936648, and was not shown in Table 3. . Further, in the same manner as in Example 1, the heat resistance was evaluated by TG/DTA. The results are shown in Table 4. Example 7 Using diethoxy sand yard 9.86 g (60 mmol), trimethoxyethyl decane 8.89 g (60 mmol), dimethoxy dimethyl decane 29.93 g (249 mmol), 1,1,3,3 - Tetramethyldioxane 3 6 · 40 g ( 2 7 1 mm ο 1 ), 2-propanol 192.098, xylene 384.188 and 1.28% hydrochloric acid 20.61 were obtained as in Example 1 to obtain an almost colorless liquid ( Hereinafter, it is referred to as "polyoxyalkylene (P7)") 42_28g. The number average molecular weight (??) of the polyoxyalkylene (P7) measured by GPC was 700. Further, the result of measuring the viscosity at 25 ° C was 13 mPa·s. Further, the results of the analysis of 1H-NMR (nuclear magnetic resonance spectrum) of polyoxyalkylene (P7) are as follows. 1 Η-NMR ( C 6 D 6, δ (ppm ) ) : - 0.2 ～ 0 _ 6 ( br, S i - C Η 3 ), 0.9 ～ 1.5 (br, OCH (CH 3 ) 2, OCH 2 CH 3 ) , 3.5 〜 4.1 (br, OCH2CH3), 4.1 to 5.5 (br, OCH (CH3) 2, Si-H), 5.7 to 6.4 (br, CH = CH2). The reaction rate of 1,1,3,3-tetramethyldioxane by 1H-NMR was 45%. Further, in the polyoxyalkylene (P7), an alkoxymethyl group (isopropoxy fluorenyl group and ethoxy fluorenyl group) which was not reacted or formed was observed. The ratio of alkoxyfluorenyl (alkoxy) can also be determined by 1H-NMR. These analyses are shown in Table 2, 200936648. The molar ratio of each of the constituent units described in Table 1 and Table 2 is determined by the average number of each constituent unit contained in one molecule of polyoxymethane, and is shown in Table 3. Further, in the same manner as in Example 1, the heat resistance was evaluated by TG/DTA. The results are shown in Table 4. φ Example 8 49.28 g (300 mmol) of triethoxymethane, 29.65 g (200 mmol) of trimethoxyvinyl decane, 0.048 g (0.4 mmol) of dimethoxy dimethyl decane, 1,1,3,3- A nearly colorless candy-like substance was obtained in the same manner as in Example 1 except that tetramethyl oxazepine 0.42 § (3.1111111 〇 1), 2-propanol 116.01 g, xylene 23 2.02 g, and 1.28% hydrochloric acid 27.51 g were used. Hereinafter, it is referred to as "polyoxyalkylene (P8)") 33.76 g. The result of measuring the Μη of the polyoxyalkylene (P8) was 1 300. Also, the viscosity at 25 °C cannot be measured. Further, the results of 1H-NMR analysis of polyoxyalkylene (P8) are as follows: 〇'H-NMR (C6D6,6 (ppm)): -0.2 to 0 · 6 (br,S i - C Η 3 ), 0.9 to 1.5 (br, OCH (CH3) 2, 〇CH2CH3), 3.5 to 4.1 (br, OCH2CH3), 4.1 to 5.5 (br, OCH (CH3) 2, Si-H), 5.7 to 6.4 (br, CH = CH2). The reaction rate of 1,1,3,3-tetramethyldioxane by 1H-NMR was 64%. -51 - 200936648 Further, in the polyoxyalkylene (P7), an alkoxythio group (isopropoxy fluorenyl group and ethoxy fluorenyl group) which was not reacted or formed was observed. The ratio of alkoxyfluorenyl (alkoxy) was also determined by 1H-NMR. These analyses are shown in Table 2, which are shown in Table 1, and the molar ratio of each constituent unit shown in Table 2, and the average number of each constituent unit contained in one molecule per polyoxyalkylene was determined, and Shown in Table 3. Further, in the same manner as in Example 1, the heat resistance was evaluated by TG/DTA. The results are shown in Table 4. Comparative Example 1 246.41 g (1500 mmol) of triethoxy decane, 74.12 g (500 mmol) of trimethoxyvinyl decane, and 67.16 g (500 mmol) of '1 - propyl 1,1,3,3-tetramethyldioxane. In the same manner as in Example 1, except that 500 g of an alcohol, 1000 g of toluene, and 1.28% of hydrochloric acid were used, 154.60 g of a liquid which is almost colorless (hereinafter referred to as "polyoxane (Cl)") was obtained. The result of measuring the Μη of the polyoxyalkylene (C1) was 1,700. Further, the result of measuring the viscosity at 25 ° C was 5 2 2 mPa*S (refer to Table 1). Further, the results of 1H-NMR analysis of polyoxyalkylene (C1) are as follows: 〇1 Η _ NMR (C 6 D 6, δ (ppm ) ) : - 0.2 〜 0 · 6 ( br, S i - C Η 3), 0.9~1.5 (br, OCH(CH3) 2 ' 〇CH2CH3) ' 3.5 ~ 4.1 (br, OCH2CH3 ), 4.1 to 5.5 (br'OCH (CH3) 2, Si-H), 5.65 to 6.5 (br , CH = CH2). -52- 200936648 The reaction rate of 1,1,3,3-tetramethyldioxane by 1H-NMR was 45%. Further, an unreacted or formed alkoxy group (isopropoxy chopping group and ethoxylated sand group) was observed in the 'polyoxane (C1)'. These analyses are shown in Table 2. The 莫η described in Table 1 and the molar ratio of each constituent unit shown in Table 2 were determined as the average number of constituent units per molecule of polyoxymethane, and are shown in Table 3. Next, using the obtained polyoxyalkylene, a cured polyoxymethane was produced by two kinds of curing conditions, and the evaluation was carried out in the same manner as in Example 1. The above polysiloxane (not containing a ruthenium hydrogenation catalyst) was applied onto a glass plate by bar coating, and then heat-hardened at 130 ° C for 4 hours to obtain a cured product (cured film) having a film thickness of about 10 μm. . The fracture at this time was not confirmed. As a result of evaluation of the cured product by TG/DTA, the temperature at which the reduction of 5% by weight under a nitrogen atmosphere (temperature rising rate of 20 ° C /min) was 670 ° C 。 . The temperature reduced by 5% by weight in an air environment is 890 °c. The results are shown in Table 4. On the other hand, the above polyoxyalkylene oxide (which does not contain a ruthenium hydrogenation catalyst) was applied onto a steel plate (SPCC-SD) by bar coating, and then heated at 130 ° C for 4 hours and then at 170 ° C for 4 hours. Alternatively, it was hardened by heating at 200 ° C for 1 hour to obtain a cured product having a film thickness of about 10 μm. The hardened material is broken. The above evaluation results are shown in Table 4. Comparative Example 2 -53- 200936648 24.64 g (150 mmol) of triethoxydecane, 22_23 g (150 mmol) of trimethoxyethane, 15.93 g (150 mmol) of dimethoxymethyl decane, and 76.29 g of propanol. In the same manner as in Example 1, except that 259.95 g of xylene, and 21.9 g of 1.28% hydrochloric acid, 28.52 g of a highly colorless liquid (hereinafter referred to as "polyoxane (C2)") was obtained. The result of measuring the Μη of the polyoxyalkylene (C2) was 1,700. Further, the result of measuring the viscosity at 25 ° C was 3 1 70 0 mPa·s (refer to Table 1). Further, the results of 1H-NMR analysis of polyoxyalkylene (C2) are as follows: 〇^-NMR (C6D6, 5 (ppm)): -0.2 -0.7 (br, Si-CH3), 0.9 to 1.5 (br, OCH (CH3) 2, OCH2CH3), 3.5 to 4.1 (br, OCH2CH3), 4 · 1 to 5.7 (br, OCH (CH3) 2, Si-H), 5.7 to 6.6 (br'CH = CH2). In the polyoxyalkylene (C2), an alkoxymethyl group (isopropoxy fluorenyl group and ethoxy fluorenyl group) which was not reacted or formed was observed. These analyses are shown in Table 2. The 莫η described in Table 1 and the molar ratio of each constituent unit shown in Table 2 were determined and found in Table 3 as the average number of constituent units included in one molecule of polyoxyalkylene. Further, in the same manner as in Comparative Example 1, the heat resistance was evaluated by TG/DTA. The results are shown in Table 4. Comparative Example 3: using 49.28 g (300 mmol) of diethoxy sand yard, 35_58 g (240 mmol) of tricarboacetate 200936648, 144.39 g of 2-propanol, 513.84 g of formazan, and 29.57 g of 1.28% hydrochloric acid, In the same manner as in Example 1, 38.61 g of a highly colorless high-viscosity liquid (hereinafter referred to as "polyoxane (C3)") was obtained. The result of measuring the Μη of the polyoxyalkylene (C3) was 1200. Further, the result of measuring the viscosity at 25 ° C was 28 1 000 mPa·s (refer to Table 1) *> Further, the results of 1H-NMR analysis of polyoxyalkylene (C3) are as follows: ❾ 1 H-NMR ( C 6D 6, δ ( ppm ) ) : 0 · 7 〜 1 · 5 ( br, OC Η ( CH3 ) 2 ' OCH2CH3 ) , 3 · 5 〜 4 · 1 ( br, OCH2CH3 ) ' 4.1 ~ 5.5 ( br, OCH ( CH3) 2,Si-H), 5.6~6.5 (br,CH=CH2) o In the polyoxyalkylene (C3), an unreacted or alkoxymethyl group (isopropoxy fluorenyl group) was observed. And ethoxylated thiol). These analyses are not shown in Table 2. Μ The ratio of Μη described in Table 1 and the molar ratio of each constituent unit shown in Table 2 was determined as the average number of constituent units per molecule of polyoxymethane, and is shown in Table 3. Further, in the same manner as in Comparative Example 1, the heat resistance was evaluated by TG/DTA. The results are shown in Table 4. -55- 200936648 Polyoxane viscosity (mPa · s) ITi σν 1 <N CN in 31700 281000 C3 1300 1100 1200 1800 1800 1500 〇 1300 1 ;1700 1700 1200 Secret in 41EI M, D, TM, D, TM, D, TM, D, TM, D, TM, D, TM, D, TM, D, THH cT H Type CN Oh Dh 2 in Oh Ph 00 Oh 1—M rj G 矽 compound loading (mole Ratio) 矽 compound (M) K) Art 1 1 fr Jiff rA S ί^· m 1 1 1 1 1 1 义1 1,1,3,3-Tetramethyldioxane CO 〇1 1 1 CN ^ Ti — 0.031 1 1 矽 compound (D) Dimethoxy dimethyl decane Ο (N 〇00 inch o 1 1 1 inch · 0.002 1 1 1 dimethoxymethyl decane I 1 1 〇1·^ *T ) 1 1 1 1-H 1 矽 compound (T) Iflig 111 sTM 1 1 d 1 1 1 1 1 1 1 1 trimethoxyvinyl decane OO o 1 1 1 »—H inch triethoxy decane mmm inch inch In Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3

-56- 200936648 The 1,1,3,3-tetramethyldioxane and 1,3-diethylenetetramethyldioxane described in the "Antimony Compound (Μ)" in Table 1 are in one molecule. It contains 2 deuterium atoms, so when the loading amount is 1 mol (mol ratio), 2 mol of the structural unit 表 of Table 2 is formed.

-57- 200936648 £ Composition of polyoxyalkylene (Mohr ratio of each constituent unit) Moh ratio of unreacted or formed alkoxy groups EtEi/2 I 0.05 0.08 0.07 0.05 0.05 0.05 0.05 0.05 0.01 0.21 Ci • £ - - Η 0.30 0.38 0.35 0.24 0.27 0.28 0.15 0.25 0.25 0.08 0.75 Μ • Ν Πίπΐ Structural unit Μ lt <Ν Ο Ο Ο 0.79 0.76 0.94 Ο Ο Ο Ο Ο Ci Ο (Λ rs Ε X 1.28 1.03 Ο Ο Ο 0.02 0.90 Ο Ο ΠΠ±Γ Μ Ν•Ν k Structural unit D Me2Si〇2/2 0.48 (Ν Ο 0.48 Ο Ο Ο 4.15 0.002 Ο ο Ο C? GO X Ο Ο Ο 0.48 Ο Ο Ο ο •n <Π Ffl 听结构单位Τ ViPhSi03/2 Ο Ο 0.15 Ο Ο Ο Ο Ο Ο ο ο 1 ViSi〇3/2 1 0.85 Ο ο ο 寸 1 HS1O3/2 1 mm inch inch τ—η Κ 嫲CL, (Ν & Η m α, 2 〇Η 00 00 〇Η U rj rn Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 _Ε辄:JdTwKI:UJ, sfr: ΦΙΛΙ ,W浒#:: rd ,«褰κι: !Λ οΟ -58- 200936648 Table 2, structural unit T and structure list The molar ratio at position D is the enthalpy assumed for the reaction of the corresponding compound on the chemical quantity. Further, the molar ratio of the structural unit oxime and the alkoxy group is calculated from the iH-NMR analysis data. The molar ratio of the alkoxy groups was determined in Examples 1 to 3, 7 and 8, and Comparative Examples 1 to 3 from the peaks derived from the vinyl group in the structural unit enthalpy and the peak area ratio from the methyl group in each unit. Further, in Examples 4 to 6, the peak ratio from the methyl group in the structural unit D and the peak area ratio from the methyl group in each unit were obtained.

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Claims (1)

H-Si〇3/^ (A-(RVSiO buckle 200936648 X. Patent Application No. 1. Polyoxane which is a substance having three hydrolyzable groups (T) and having two hydrolyzable groups) The compound (d) and the hydrolyzable group of the oxime compound (M) are hydrolyzed and polycondensed by a polycondensation reaction characterized by at least the above ruthenium compound (T), the above ruthenium compound (D) and the compound (M). 1 having an anthracene hydrogen group, 0 at least one of the above-mentioned anthracene compound (T), the above-mentioned anthracene compound (D), and a compound (M) having a carbon-and-hydro group which can be hydrogenated, and the above-mentioned polyoxyalkylene has an anthracene The carbon-carbon group, the hydrazine group and the alkoxy fluorenyl group of the hydrogenation reaction have a number average molecular weight of 500 Å. 2. The polysiloxane of the first aspect of the patent application, which contains the formula (1) Composition; [Chemical 1 七 02/2) (R3-Pack 01/2) (R5〇i/2 [In the formula (1), A is a carbon-carbon unsaturated carbon number 2 to 10 having a hydrogenation reaction. The organic group, R1 is an alkylene group having 1 to 20 carbon atoms, a divalent aromatic group of -20 or a divalent alicyclic group S having a carbon number of 3 to 20 of 0 or 1, and R 2 is a hydrogen atom and a carbon number of 1 to 2. 10 alkyl, or The carbon-carbon unsaturation group of the carbon-carbon unsaturation group may have the same or different R2 in the organic group having 2 to 10 carbon atoms, and R3 is a hydrogen atom or has a -63-fluorene compound having 1 and the above-mentioned ruthenium carbon is not obtained. Saturated unsaturated ^ 20000 The following one (1) and the base carbon number 6 妄 group, η has a sandable (1 point of sandable hydrogen 200936648 reaction carbon-carbon unsaturated group of carbon number 2~10 organic group, R4 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an organic group having 2 to 10 carbon atoms which has a carbon-carbon unsaturated group capable of hydrogenation reaction (R4 in 1 molecule may be phase N or different) 'R5 is the base of carbon number 1~6, v, X, y and z are positive ' w is 〇 or positive ' o.ooi each x/(v + w) $2,0.01Sy/( V + W) &gt O.Ol^z/ ( V + W + X + y) $1; however, when w=〇, at least one of R2, R3 and R4 is a carbon number of a carbon-carbon unsaturated group having a hydrogenation reaction 2 to 10 organic group] 3. A method for producing a polyoxyalkylene, which is a method for producing a polyoxyalkylene according to the first aspect of the patent application, characterized in that it contains three hydrolyzable groups. Bismuth compound (T) with 2 hydrolysis The first step of the hydrolysis/polycondensation reaction of the hydrazine compound (D) and the hydrazine compound (M) having one hydrolyzable group in the presence or absence of an organic solvent, the hydrazine compound (T), At least one of the ruthenium compound (d) and the ruthenium compound (M) has an anthracene hydrogen group, and at least one of the ruthenium compound (T), the ruthenium compound (D), and the ruthenium compound (μ) has a ruthenium. A carbon-carbon unsaturated group of a hydrogenation reaction. 4. The method for producing a polyoxyalkylene according to claim 3, wherein the hydrolyzable group of the sand compound (T) is an alkoxy group, and the hydrolyzable group of the antimony compound (D) is an alkoxy group. The hydrolyzable group which the sand compound (μ) has is an alkoxy group or a decyloxy group. 5. The method for producing a polyoxyalkylene according to claim 3 or 4, wherein after the first step, the solvent is contained in a solvent of 200936648 aromatic hydrocarbon having a boiling point of 9 〇 or more, The second step of distilling off the water. 6. The method for producing a polyoxane according to any one of claims 3 to 5, wherein the polyoxasiloxane has a composition represented by the following general formula (2): (2) In the formula (2), A is an organic group having 2 to 10 carbon atoms having a carbon-carbon unsaturated group capable of hydrogenation, and R1 is an alkyl group having 1 to 20 carbon atoms and a carbon number of 6 to 20. a divalent aromatic group or a divalent alicyclic group having 3 to 20 carbon atoms, η is 0 or 1, R 2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon-carbon having a hydrogenation reaction An organic group having 2 to 10 carbon atoms of an unsaturated group (R2 in one molecule may be the same or different), and R3 is a hydrogen atom or a carbon number of a carbon-carbon unsaturated group having a hydrazine hydroquinone reaction. The organic group of 10, R 4 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an organic group having 2 to 10 carbon atoms which has a carbon-carbon unsaturated group capable of hydrogenation reaction (R4 in 1 molecule may be the same) Or different), R5 is an alkyl group with a carbon number of l~6, v, x, y, and Z are positive numbers, w is 0 or a positive number, 0.001Sx/(v + w) $2, 0.01Sy/( v + w) > O.Ol^z/ ( v + w + x + y ) SI; however, when w=0, at least one of R2, R3 and R4 is a carbon having a carbon-carbon unsaturated group capable of hydrogenation reaction Number 2 to 10 organic groups]. 7. A method for producing a polyoxymethane cured product, which comprises a polyoxyxane of -65 to 200936648, as in the first aspect of the patent application, in the non-existence of a catalyst for hydrogenation reaction, 15 TC or more 7 〇〇. (: The following steps are carried out to heat. 8. A method for producing a polyoxymethane cured product, which comprises the following steps and is carried out in the following order; The polyoxyalkylene is heated in a non-existent application of a catalyst, at a temperature of 50 ° C or higher and less than 150 ° C, and at a temperature of 15 (TC or higher and 700 ° C or lower). -66- 200936648 No. · Ming said that there is no simple: the number is the map of the map element: the table pattern represents the book, the one or two fingers c C ' seven ❹ eight, if there is a chemical formula in this case, Please reveal the chemical formula that best shows the characteristics of the invention: flawless